Organic tin compound containing catalyst system useful for producing epoxy compounds

ABSTRACT

CATALYST SYSTEM USEFUL FOR PRODUCING EPOXY COMPOUND CONTAINING (1) AT LEAST ONE ORGANIC TIN COMPOUND AS A FIRST COMPONENT HAVING AT LEAST ON HYDROXYL GROUP OR A COORDIATION GROUP WHICH IS CAPABLE OF BEING CONVERTED TO A HYDROXYL GROUP IN THE PRESENCE OF WATER OR HYDROGEN PEROXIDE AND (2) A SECOND COMPONENT SELECTED FROM COMPOUNDS OF MOLYBDENUM, TUNGSTEN, VANADIUM, SELENIUM, BORON AND MIXTURES THEREOF.

United States Patent 3,806,467 ORGANIC TIN COMPOUND CONTAINING CATALYSTSYSTEM USEFUL FOR PRO- DUCING EPOXY COMPOUNDS Yoshihiro Watanabe, Kobe,Toshio Nishizawa, Takatsuki,

and Jiro Kobayashi, Ibaraki, Japan, assignors to Sumitomo Chemical C0,,Ltd., Osaka, Japan No Drawing. Original application Mar. 10, 1970, Ser.No. 18,335. Divided and this application Sept. 30, 1971, Ser. No.185,369

Int. Cl. C07d 1/08, 1/06 US. Cl. 252--429 R 2 Claims ABSTRACT OF THEDISCLOSURE Catalyst system useful for producing epoxy compoundcontaining 1) at least one organic tin compound as a first componenthaving at least one hydroxyl group or a coordination group which iscapable of being converted to a hydroxyl group in the presence of wateror hydrogen peroxide and (2) a second component selected from compoundsof molybdenum, tungsten, vanadium, selenium, boron and mixtures thereof.

This is a division of application Ser. No. 18,335, filed Mar. 10, 1970.

This invention relates to a novel method of oxidizing organic compoundsand more particularly to a novel process for producing epoxy compoundsfrom olefins in the presence of a special catalyst.

Epoxy compounds play an important role in the industry as intermediatematerials for industrial chemicals, synthetic resins, rubbers, etc.

There are already known many methods of epoxidizing olefins. Forexample, the most typical industrial method is the gas phase oxidationof ethylene. However, such method can proceed in considerably highyields for ethylene which has the simplest chemical structure amongolefins but is low in the yield for other olefins, particularlypropylene, so that it has been found to be difficult to industrializesuch method in respect to olefins other than ethylene.

The most widely used method of epoxidizing olefins is the so-calledchlorohydrin method long known in the art. However, this method has suchdrawbacks as the high cost required for large electrolytic equipment,corrosion of the apparatus and the waste of expensive chlorine.Therefore, a more economical method has been strongly hoped for.

From such viewpoint, some improved methods have been proposed. Thus, forexample, there has been proposed a method wherein a strong activesubstance such as a peracid, particularly peracetic acid is used as an.epoxidizing agent for olefins. However, this method has variousdrawbacks that peracetic acid itself is produced from hydrogen peroxideand acetic acid or acetaldehyde and oxygen; and therefore its productioncost is high, that peracetic acid is explosive and there is required aspecial care for its handling.

Further, there is also known an in situ method (I.E.C. 47, 147) whereinhydrogen peroxide is utilized as an epoxidizing agent in the presence ofan acid catalyst together with a fatty acid. However, there is a greatdisadvantage that, due to the use of the strong acid catalyst, theformed epoxide is hydrolyzed partially to become glycol which is thenpartially esterified together with a fatty acid.

Also newly proposed is a method (U.S. Pats. 3,360,584, and 3,351,635)wherein an olefin and an organic hydroperoxide are brought into contactwith each other in the presence of a metallic compound comprisingvanadium, molybdenum, tungsten, selenium or mixture. However, suchmethod has drawbacks that the organic hydroperoxide itself is expensive,and that, in principle, a corresponding alcohol in an amount equivalentto the formed epoxide compound is by-produced and therefore theeconomical merit of this method is likely to be influenced by themarketability of the by-product.

As described above, the conventional methods of epoxidizing olefins havebeen not fully satisfactory.

Recently hydrogen peroxide has come to be economically mass-produced dueto the development of improved oxidation of secondary alcohols orquinone compounds and has come to be very cheap particularly in thestate before purification or concentration.

Therefore, some attempts to utilize hydrogen peroxide directly as anepoxidizing agent have been made, e.g. Bull. Chem. Soc. Jap. 42, 1604,69 (I), J. Org. Chem. 22, 1682, 57 (II). In the former method (I), theepoxy compounds of C C cyclic olefins are produced mainly by oxidationwith hydrogen peroxide in the presence of a selenium dioxide catalyst.However a very large amount of the catalyst is required and thispublication does not mention the epoxidability of aliphatic olefins. Inthe method (II), grycohol of C cyclic olefin is produced mainly in thepresence of such metallic compounds as of H WO as catalyst.

However, a small amount of epoxy compounds have been isolated as onlyintermediates. What can be generally said is that, with such simplecatalyst systems, the epoxidizing activity of hydrogen peroxide is solow that, as mentioned also in the above literatures, the formation of asmall amount of epoxy compound is recognized only on very specificcompounds, especially cyclic compounds, and the reaction proceeds to adiol in most cases. From such viewpoint, the investigation to usehydrogen peroxide directly for an epoxidation has not been establishedpractically. Therefore, it has been necessary to convert hydrogenperoxide into a peracid as mentioned hereinbefore or to employ anorganic hydroperoxide.

An object of the present invention is to provide an advantageous andindustrially practical method wherein, by the adoption of newlydiscovered catalyst system, hydrogen peroxide may be used effectivelyand directly as an epoxidizing agent for the epoxidation of olefins.

It has now been found that, when a catalyst system having the belowdescribed specific composition is used dissolved or suspended in thereaction solvent and olefin, hydrogen peroxide can be advantageouslyused as an epoxy oxygen source.

According to the present invention, there is used a catalyst systemcomprising a combination of (1) at least one tin compound as a firstcomponent and (2) a second component selected from the group consistingof compounds of vanadium, molybdenum, tungsten, selenium, and boron, andmixtures of any two or more of these compounds.

As for the tin compound which is the first component, both organic tinand inorganic tin compounds may be used.

As for the organic tin compounds, there can be exemplified tin compoundshaving at least one hydroxyl group or having a coordination group whichcan be converted to a hydroxyl group in the presence of water orhydrogen peroxide. More particular examples are those having any of thefollowing formulae:

wherein each of R R R R R and R represents an alkyl group, aralkylgroup, phenyl group, phenoxy group, alkoxy group, hydrogen atom,carbonyl group, nitrile group, hydroxyl group, acyl group, halogengroup, --SR or O-R and R represents an alkyl or phenyl group. It is alsopossible to employ a synthesized solution or extract containing such tincompound.

Examples of the inorganic tin compounds, are tin chloride, tin sulfide,sodium stannate, tin oxide and organic acid salts of tin.

Generally, an organic tin compound has an activity much higher than thatof an inorganic compound.

The second component of the catalyst system of this invention isselected from organic and inorganic compounds containing molybdenum,tungsten, vanadium, selenium or boron. Examples of the soluble secondcomponent are naphthenates, stearates, octoates, carbonyls,acetylacetonates polyacid, and the like, of the above-mentioned metals.Examples of the insoluble second component are oxides, ammonium salts,phosphates, nitrates, sulfates, carbonates, and the like.

In case a boron compound is used as the second component, there can beenumerated 'boric acid, boron trioxide, alkylboroxin, alkoxyboroxin,boric acid esters, metallic borates, halides, carbonyl compounds, alkylboron compounds and hydrides.

Further, composite salts containing any one of molybdenum, tungsten,vanadium, selenium and boron, for example, boron tungstic acid,phosphorus molybdic acid, phosphorus tungstic acid, phosphorus vanadicacid, phosphorus selenic acid and compounds containing two or more ofthese elements may also be used.

The first component and second component of the catalyst to be used inthe present invention may be added simultaneously as mixed in advance tothe reaction system or may be added separately to the reaction system.Further, the catalyst can be used in the form of a compound or complexcompound containing simultaneously a tin atom and a molybdenum,tungsten, vanadium, selenium or boron atom.

However, in the absence of any of these two components, that is, withthe first component or second component alone, no sufiicient epoxidizingactivity can be obtained (refer to Reference examples givenhereinafter). Thus, for example, even if a small amount of the abovedescribed tin compound is added into a mixture of hydrogen peroxide andcyclohexene and the mixture is heated to 60-80 C., substantially nochemical change occurs. Some tin compounds would senve rather asstabilizers for hydrogen peroxide. Further, on the contrary, it is knownthat, in case a small amount of only tungstic acid is added, a largeamount of a diol or ether is produced, and substantially no epoxycompound is produced (J. Org. Chem., 22, 1682 (1957)). In sharp contrastthereto, if both are made to coexist in the reaction system, asurprisingly large amount of an epoxy compound is produced.

For the concentration of the catalyst, each of the first and secondcomponents can be selected independently over a considerably wide range.Although the ratio of the first component to the second component is notindependent of reaction products, the ratio may be varied widely. But,the ratio of atom of the first component is preferable more than that ofthe second component. The element of the second component per one tinatom is 10.00l, preferably 0.1-0.01. Generally, a concentration (byweight ratio) of the mixture of the first component and the secondcomponent in the reaction system is about 1/l0,000 to 1/ 10, preferablyabout 1/ 100 to 1/1,000. However, generally, in case a boron compound isused for the second component, the higher the concentration of boron,the better the result. It is desirable therefore to use such boroncompound as a saturated solution, if possible.

As regards the working mechanism of the catalyst system of the presentinvention, there have been recognized some phenomena which can explainthat the first component, the second component and hydrogen peroxideform an active complex compound effective or favorable to theepoxidizing reaction.

The solvent to be used in carrying out the method of the presentinvention may be selected from a considerably wide range of ordinaryorganic compounds, provided that they do not quickly react with theolefin, hydrogen peroxide and/or catalyst. However, it has been foundthat, in some solvents, the compatibility with olefin and hydrogenperoxide is low so that the reaction system separates into a pluralityof phases and, in case the reaction is continued for a long time or incase the reaction temperature is elevated, the tin compound is depositedon the wall and bottom of the reaction vessel.

From the industrial viewpoint, when the solubility and stability of theraw material olefin and catalyst system and the stability of hydrogenperoxide are considered, the proper selection of the solvent isimportant to the method of the present invention.

It has been found that, in case the below mentioned [four operations arecarried out in respect of various typical solvents, the stability oforganic tin hydroxide and hydrogen peroxide is remarkably influenced, asdemonstrated in Table 2 to be indicated hereinlater:

Operation 1: (Me) SnOH and hydrogen peroxide were dissolved at the roomtemperature.

Operation 2: Cyclohexene was added to the above mentioned solution.

Operation 3: The resulting solution was then warmed up to 60 C.

Operation 4: Then the solution was allowed to stand at the roomtemperature for 3 days.

It has been observed from these results of the operations that generallyalcohols such as straight chain a1- cohols, polyhydric alcohols andcyclic alcohols are preferable as solvents for the method of the presentinvention, but epoxides, ketones and furfurals can be also used. Theheat of reaction in the epoxidation is considerably high so that themaintenance of the reaction temperature is an important requirement inthe case of industrially working the invention. However, by properlyselecting the solvent from among these solvents, the reactiontemperature can be maintained constant by utilizing the boiling point ofthe solvent.

From the above, it will be understood that, in order to efficientlycarry out the method of the present invention, the selection of thesolvent is important.

In carrying out the method of this invention, there may be usedcommercial grade of hydrogen peroxide as such, and generally an aqueoussolution of such hydrogen peroxide of a concentration of 10 to may beused. However, as an industrially cheap hydrogen peroxide source, it isadvantageous to use an unconcentrated unpurified intermediate productobtained by a known process for the production of hydrogeniperoxide.

For example, it is known that hydrogen peroxide and ketone are obtainedby atmospheric oxidization of a secondary alcohol (US. 'Pat. No.2,871,101). However, the hydrogen peroxide obtained by such process ismarketed in the form of an aqueous solution generally prepared throughsuch steps as distillation, concentration and purification. By suchafter treatments, the price of hydrogen peroxide rises so surprisinglyas to obstruct the industrial utilization of hydrogen peroxide. On theother hand, in the method according to the present invention, alcoholsand ketones are very favorable solvents giving results rather morefavorable of an aqueous solution. Therefore, the reaction productcontaining hydrogen peroxide, alcohol and ketone obtained by the oxidation of a secondary alcohol can be used directly as such or as more orless concentrated as a source of hydrogen peroxide for the method of thepresent invention.

Further, another known process for producing hydro gen peroxide by theoxidation of an anthraquinone derivative may also be advantageouslycombined with the epoxidation according to the present invention.

Thus, it is possible to combine the method of the present invention withan already known conventional process for the production of hydrogenperoxide, so that the method may be worked industrially advantageously.

Examples of the compounds which can be epoxidized by the method of thepresent invention are olefinic compounds such as propylene, normalbutylene (1 or 2), isobutylene, 1,3-butadiene, allyl alcohol, methylallyl alcohol, allyl chloride, isooctane, styrene and a-methyl styrene:unsaturated fatty acids such as soybean oil, oleic acid, etc.; cyclicolefins such as cyclohexene, 4- cyanocyclohexene, cyclooctadiene andcyclododecatriene; and the like.

'It is preferable, by taking the safety into consideration, to selectthe initial concentration of hydrogen peroxide in the reaction mixtureto be about 1 to 50% by weight. The concentration of the olefin withrespect to the hydrogen peroxide may be varied over a wide range. Thoughnot critical, it is generally economically desirable that the mol ratioof the olefin to hydrogen peroxide be 1:30 to 30:1.

The temperature to be used in the present reaction varies over a verywide range depending on the properties of olefin to be epoxidized, theconcentration of the catalyst and the ratio of the olefin to thehydrogen peroxide. However, it is generally -20 C. to 150 C., preferably0 C. to 120 C. or particularly 20 C. to 100 C.

The reaction is conducted under a pressure sufficient to maintain aliquid reaction phase. The reaction may also be conducted below theatmospheric pressure but usually a pressure of about 1 to 100atmospheres is desirable.

The reaction time also varies depending on the prop erties of olefin tobe epoxidized, the concentration of the catalyst, the ratio of theolefin to the hydrogen peroxide, the reaction temperature and thedesired extent of the reaction. It is possible to carry out the reactionwithin such short time as about one minute or for a long time such as100 hours or longer.

Thus, as explained herein above, this invention provides a novel,economical and effective method for the epoxidation of olefins. Thepresent invention is fully distinguished from conventional methodswherein hydrogen peroxide is once converted to a peracid or organichydroperoxide and is then used for the epoxidation. This invention hasthus opened a way to the production of an epoxy compound by the directuse of hydrogen peroxide, due to the discovery of a novel and veryeffective catalyst system. The method of the present invention does notrequire the use of corrosive materials, is not bound by theby-production of any other industrial chemicals chemicals and istherefore very advantageous to the industry.

Since there is no acid catalyst which promotes the hydrolysis of theformed epoxy compound in the reaction system, the undesirable formationof glycols is remarkably prevented. This is one of the features of themethod of the present invention.

6 The present invention will be further explained by referring to thefollowing examples.

Example 1 There were charged 11 g. of n-propanol (as a solvent), 4.0 g.of cyclohexene and 12 g. of 90% hydrogen peroxide in a 50 cc. glassflask equipped with a reflux condenser and stirrer. Then 0.1 g. oftrimethyl tin hydroxide Me SnOH and 0.01 g. of acetylacetone molybdenumsalt MoO (AcAc) were added thereto as catalysts. The mixture was causedto react at 50 C. for 9 hours.

After the reaction, the hydrogen peroxide was colored with potassiumiodide and was titrated with a 0.1 N sodium thiosulfate solution toquantitatively determine the unreacted hydogen peroxide.

The unreacted cyclohexene and produced cyclohexene oxide were analyzedby gas chromatographs.

As a result, the formation of 0.90 g. of cyclohexene oxide was observed.This corresponds to 90% based on the reacted hydrogen peroxide and 95%on the re acted cyclohexene.

Examples 2 and 4 to 14 and Reference Examples 1 and 2 (the use ofvarious olefins and various combinations of catalysts) Experiments wereconducted in substantially the same manner as in Example 1 except thatthe combinations of the kinds of olefins and catalysts and some reactionconditions were changed. The results of the experiments are collectivelyindicated in Table 1.

Example 3 (the use of an extract) The procedure of Example 1 wasrepeated except that a catalyst prepared in the following manner wasused. Thus 1 g. of tributyl tin chloride was dissolved in an aqueoussolution containing 0.5 g. of sodium hydroxide, and was made to react atC .for 2 hours. Then the reaction product was extracted with ether. Theresults obtained by the use of $4 the amount of the oil layer togetherwith 0.01 g. of MoO (AcAc) to the reaction system are shown in Table 1.

Example 15 (the use of propylene) There were charged 9.0 g. of ethanol(as solvent) into a glass autoclave of a capacity of 50 cc. Further, 4.2g. of 70% hydrogen peroxide, 0.08 g. of trimethyl tin hydroxide and0.014 g. of MoO (AcAc) were added thereto and then the mixture wascooled in a Dry Ice-methanol bath. After evacuation, there wereintroduced and dissolved 3.8 g. of propylene. The autoclave was dippedin a water bath at 40 C. and the mixture was allowed to react for 20hours while being stirred. The results of the experiment are shown inTable 1.

Examples 16, 17 and 18 (the use of various other olefins) Reactions wereconducted in the same manner as in Example 15 except that butene-l,isobutylene and butadiene (1,3) were respectively used as olefins.

The results of the experiments are shown in Table 1.

Examples 19 to 34 (effect of reaction solvent) Operation 1: 1 ml. ofeach of various solvents was put into a test tube of a capacity of about10 cc. Then 0.01 g. of trimethyl tin hydroxide and 0.1 ml. of hydrogenperoxide were added thereto and the solubility was observed at the roomtemperature.

Operation 2: 0.5 ml. of cyclohexene was added to the solution of theOperation 1 and change in solubility was observed.

Operation 3: The solution of the Operation 2 was heated on an oil bathand, after 3 hours, the solubility was again observed.

Operation 4: The solution of the Operation 3 was cooled to the roomtemperature and was left for 3 days and the solubility was observed.

The results are shown in Table 2.

TABLE 1 Hy- Reaction Olefin drogen tempera- Reaction Yield of peroxideture time epoxide Type G. (g.) Catalyst 0.) (hrs.) (g.) RemarksReference example:

1 Oyclohexene 4. 1. 2 M0Oz(A0A0)2 50 9 0.03 9 do 4. 0 1.2 HzWO; 50 90.05 Example:

1 dn 4.0 1.2 M0Oz(A0A0)2, MeaSnOH 50 9 0.90 Selectivity 90%. 2 (in4.0 1. 2 M003, MeaSnOH 50 9 0.88 i 4. 0 1. 2 M0O2(AOA0)2, BuzSnOH 50 90. 80 4 An 4.0 1.2 HzWOz, MeQSnOH 50 9 1.4 Selectivity 87%. 5 dn 4. 0 1.2 V0 (AcAc)z, MegSnOH 50 9 0. 02 6 r1n 4.0 1.2 MoOz(AcAc)z, MezSnOH 6012 0.80 Glycol 0.1 g. 7 Isooctane 7. 4: 4. 2 M002(AGAO)2, MeaSnOH 50 50. 34 8 Styrene 8.0 1. 6 M0O2(A0A0)z, MegSnOH 50 24 0. 9Hyaneeyclohexene 9.0 4.2 MOOz(AGAC)-z, MeaSnOH 50 4 0.50 10Cyolnnnfqfiiene 8. 0 1. 6 MOO2(ACAO)2, MezsnOH 50 24 1. 9 11Cyelododecatriene 1.4 1.6 M0O2(A0A0)2, MGQSHOH 50 24 0.85 12. Allylchlorlde 8.0 1.6 M0O2(A0A0)2, MezSnOH 50 24 0.85 Selectivity 83%. 13.Ethyl vinyl ethe 8.7 1.6 MOO2(ACAC)2, MeaSnOH 50 24 0.30 Selectivity83%.; 14 Allyl alcohol 8.6 1. 6 M0Oz(AOA0)z, MegSnOH 50 24 0.32 1';Propylene 3. 8 4. 2 M00z(AeAc)2, MezSnOH 40 0.21 IR Butene-1 2. 6 1. 6MoO2(AcAc)2, MegSnOH 20 0.31 17 Isobutene 3. 6 4. 2 Mo0z(AcAc)z, MeBSnOH40 20 0.47 IR 1,3-bufarliena 2. 4: 1. 6 M0O2(AcAc)2, MegSnOH 4O 20 0.

1 Selectivity: Mol percent of formed epoxide based on reacted hydrogenperoxide. 3 Formation of monoepoxide.

TABLE 2 Operation Example number Solvent 1 2 3 4 19 (3H InsolubleInsoluble Insoluble Insoluble.

21... C014. do--- do--. Soluble..-..-."..-. White turbid. 22 CH OHHighly soluble.. Highly soluble-. Highly soluble.. Highly soluble.

Soluble Soluble Soluble Soluble.

24 O '.-...dO...-:;...;..'.--d0--.-;;..-;- White turbid-... Whiteturbid.

HaCC-(|) 25 0H .---..do Y (10.. Soluble. Soluble.

26 (i-pr)aO. Insoluble- Insoluble- White turhid..... White turbid. 27./C:H4\ Highly soluble.. Highly soluble.. Highly soluble.. Do.

28. H O\ ...do.--..-. do....- Soluble Soluble.

Highly soluble-. Highly soluble.- Highly soluble Highly soluble. Whiteturbid. White turbid White turbid.

Highly soluble 0- o Pyridine do. Do.

Propylene glycol. do .do Highly soluble. Glycerin- .do. Do.

Example 35 (catalyst) 01 B112 Sn There were charged 6 g. of isopropylalcohol (as solvent), 2.46 g. (30 mmols) of cyclohexene and 5 g. of an Oisopropyl alcohol S n of hy r g n peroxide were added thereto ascatalysts. The mixture was allowed taining 1.02 g. (30 mmols) ofhydrogen peroxide] into to react at 53 C. for 1 hour. The product wasanalyzed in a 50 cc. glass flask equipped with reflux condenser the samemanner as in Example 1. As a result, the formaand stirrer. Then 2.7 mg.of acetylacetone molybdenum tion of 7.3 mmols of cyclohexene oxide wasobserved. salt MoO (AcAc) and 150 mg. of dibutyl tin mono- Thiscorresponded to selectivity of 81% based on the chlorohydroxide reactedhydrogen peroxide and 94% on the cyclohexene M 00405 503m 3025 A 0 v 03m000802000 "A N v 0095 Hmfivgflo 0030 rmfizmflum 4335M CO 60300 350 0535Fwd 603004 Q50 308 SC #00030 0300003 8 0036 0 8 8 8 0 8 8 .5002 880500000 0 5 E 8 8 18000 5020 0 0 0 8022mm 8 8 80 8 8 0 0050 88W aoveow m0H0 3.1M: 8 8H 0 0 8 0 88 8 $8 "0340020 68 Mmovcow m 0 8 80 880 2 0 8 88 0 8 8 8 0 00300180 000000 0 0 008 8 00 8 2 3 8 88 88W 68$ 80 500000 00 E 8 8 80 0 0 0 8 8 N8 08 8 8 0 000m 8C 8000000 880 Q0 8 8 AScEiEB o 8S 8 0 0 8 8 $8 500 05 0 80 8000000 0 0 008 0 8 2 8H 8 0 0 8 8 228 0000805 080 E0X6W m 88 8 c0 08 8 0 0 8 8 so 03.00 0 0 080 000000 0 5 0 8 08 00 8 8 8 80 8 8 0x3 555 2 80 0 00 0 0080 8 00 mm 00 0 00 mm 8 00 n 4400 2 800 5000582 8 00 0 8 c 8 8 M00 8 8 0.00 55000 00 8.0 0 00 0 00 8 08 0 8 .8 8 0 8 88 020W 5 0 400 2 8B 00 0 008 0 8 8 8 8 0 8 8 020 503 002 68 00 0 2 $008 0 8 0 8m 80 0 8 8 8 C28 2 4 55 2 620 0505 CE 0 8 c 0g 8a N 0 8 8 0 8 555 080 680 Q0 8 8 8 0 8 $0009 0? 0 vv 8 8 g 8 8 028 "0030080 650 $0 8 0 8 :0 s A@V 8 8 m8 8 8 028 5500080 Q0 8 0 8 c 8 8 8 a 8 80 8 5500080 0 0 0 008 8 8 0 8 8 8 g 8 88 08W 503 0080 62W 68 m 88 8 00 88 2 HA 8 mm 80 54 000 2 6: 000000 0 2 380 8 00 8 8 8 m0 8 8 028 5 0 4002 80 02 0 00 38 0 8 c0- 8 8 8 g 8 8 028 5540080 80 8000000 0 0 8 8 0 8800080 000 8 0020 3mm 2055 E5 0 a 02 00 .05 0mm 055w 002 @3005 2000.50020 .QZ 200800 00 00 000600 0005 00000 0008.80 18005 0000300 00000039000003 .lll'll l $23030 800000000 0033mm m 030 00 0030 20 003 00000000302000000 08000 20 00000000 000003 25. mm 2008 0 00 80 0000000 2.08 2000 0000000 8000 00 00000080. 000000000 803 0003000m 00028 000 00 000000003 0 00 0080000 00 w 000 000 00 00000000200 -0008 00 050000 00 w 0 0000B 6000000 00 2000 00m 000 00000000 00000003 00 20000 02 000020 30.50%00 0000 00 0000 0003 0000 0082000 000 0903 003 0000000 20 00 0000 0 00002000 008 000000 20 000003 05 0 00 003 00 0m 00 0008000 000 000 0 000 0.02 00 000 00000 000002 0 0090 00 mm 00 00000 -00 20 000000 .000000008000 00000000 00 3 8000 m 000 02000000 m0? 00000000 25. 00000000005 \5 00 0000 00% 0000000 030008 25. 0205 05 0000000 000 30000000000 0000000 20 005 0m 80% 00 0005 020 000000 0 M5 0 0000 00 00a 000.83 00 000 820 0 00 :03 00000 20 00 00mm? 820 0 90000 B 0008 0000000 00000 00000000 00 m0 Ao000000 00n0 n0v 5 00 w 200020 88000000 00 000000800000 0000030 0000: 00 80 20v 0m uiswxm m 030m. 00 03000 000 030 25.2803 00 80 000005 0008 20 00 0 000000 00% 0008000 00000000 00 0000000 -000 0000000000 25. 0003 0003 00003000 0 00000 00.5 820 00 E00 00 000000000000 80 3 033000 025 0000000 00 0008 00200000 00003 000 00 000 30300000000 003 0006 00030000 000 000000.. 000 000000 0 0000000 0000000 0 0000002000000 0 0000.00 00800 00B 80 00000000 000 000003 0 2 2000 0 0 000800 00 80000000 0 NS 200 000 080000 20 00 8200000000 m 8? 808000 00000800 60 0$ 20 00000 00000 20 83 000 00000 00000000 00.0 000003 8000 0000000 0 00 0 32 00003000 00 w 0&0 00 0. 0 00206 000 0000 0 20 03 0.5 0002000 803 3200000 20 00 0000002 0 0 2 00 00m 00 0000000 0 00 28000000820 0 00 :8 8000000008 00003000000 00 m 0 0 000 0 06000 000 -0002 008000000 on: w 0m M55808 0000000 0000000 3000080 00 00 w 00 0000020003888 00 000 0 00 m 00 0 000020 03000000 00 0 m0 00000 000.5 0000mm 90050 m 0 0.0 0 080 0 20 0 00800000 20 00 8:080 00 000000000 0 0 83000000000 00003 20 00 0 0 2 5 9000000000 0 2 0 .2 00 00 0 m0 80 83 0 2 00838020 0 0000 8 000800 32 0 8000000800 00008 20 00 0 0 000 8. 00 80 2 00 00 m moifimxm m 0 0 01 9008000 030 0 20 3000 00000 20 00 80080 000 20000 0 0 00. $3 2008 00 20 00 003 30 0000 3088 mm 2088mm 00 00 000000000208 20 .6000 0 000000 203 800 00 3000009000 00 20 00 000 M00085 00 30200 m0 00 0m 8388mm The procedure of Example 1 was repeated except thaton a tin compound (the first component of catalyst) was used. As shownin Table 3, the yield of an epoxide was slight.

Example 57 (the use of boron compound as the second components) Therewere charged 12 g. of isopropyl alcohol (solvent), 4.92 g. ofcyclohexene and g. of an isopropyl alcohol solution containing 2.04 g.of hydrogen peroxide into a 100 cc. glass flask equipped with a refluxcondenser and stirrer. Then, 0.3 g. of dibutyl tin monochlorohydroxideand 0.14 g. of boron trioxide were added thereto. The mixture wasallowed to react at 60 C. for 1 hour. The product was analyzed in thesame manner as in Example 1.

As a result, the formation of 7.5 mmols of cyclohexene oxide wasobserved. The selectivity was 7.0% based on the reacted hydrogenperoxide and 9.7% on the cyclohexene employed.

Example 5 S The procedure of Example 57 was repeated except that 0.3 g.of tributyl tin chloride and 0.15 g. of boric acid were used ascatalysts.

There were formed 3.1 mmols of cyclohexene oxide. The selectivity was65% based on the reacting hydrogen peroxide and 90% on the cyclohexeneemployed.

Example 59 There were charged 50 g. of isopropyl alcohol (as a solvent)and g. of an isopropyl alcohol solution containing 5.1 g. of hydrogenperoxide into the same reactor as in Example 56. Then 0.9- g. of dibutyltin monochlorohydroxide and 0.4 g. of tributoxy boroxin as catalystswere added thereto. After a leakage test, the autoclave was cooled inDry Ice-methanol and evacuated. Then 12.6 g. of propylene were addedthereto and the reaction was conducted at 60 C. for 4 hours. Propyleneoxide was quantitatively determined in the same manner as in Example 55.Hydrogen peroxide was quantitatively determined the same as in Example1.

As a result, the formation of mmols of propylene oxide was observed. Theyield was 80% based on the reacted hydrogen peroxide.

Example 60 There were charged 90 g. of isopropyl alcohol and 0.7 g. ofAIBN (azobisisobutylonitrile) as an initiator into the reactor as usedin Example 56. The isopropyl alcohol was oxidized by introducing air.Thus the oxidation was conducted for 5 hours by introducing air underpressure during the reaction so that a reaction temperature of 130 C.and a reaction pressure of 50 kg./'cm. might be kept. After thereaction, a part of the cooled solution was taken and analyzed. Itcontained 1200 mmols of isopropyl alcohol, 150 mmols of a peroxide and300 mmols of acetone. Then, 0.7 g. of tin oxide and 0.5 g. of boric acidwere added to this solution. Propylene was introduced into the mixtureto cause reaction in the same manner as in Example 59, to produce 5mmols of propylene oxide. The selectivity was 52% based on the reactedhydrogen peroxide.

Example 61 The procedure of Example 57 was repeated except that 0.1 g.of trimethyl tin hydroxide was added instead of dibutyl tinmonochlorohydroxide. There were produced 7.2 mmols of cyclohexene oxide.The selectivity was 75% based on hydrogen peroxide and 90% oncyclohexene employed.

12 Example 62 The same reactor was used as in Example 57 except thatmethanol cooled with Dry Ice was circulated in the reflux condenser toprevent the flow out of low boiling point component.

There were charged 12 g. of isopropyl alcohol (as a solvent), 4.12 g. ofallyl chloride as an olefin and 10 g. of an isopropyl alcohol containing2.04 g. of hydrogen peroxide into this reactor. Then 0.2 g. ofbis(tributyl tin) oxide and 0.14 g. of boron trioxide were added theretoas catalysts. The mixture was allowed to react at 60 C. for 1 hour.There were obtained 1.2 mmols of epichlorohydrin. The selectivity was63% on base of the hydrogen peroxide and 83% on the allyl chlorideemployed.

Example 63 The procedure of Example 61 was repeated except that othercatalysts and solvent were employed. Thus 0.15 g. of trimethyl tinacetate and 0.14 g. of boron trioxide were used as catalysts, and 12 g.of furfural were used as solvent. There were produced 1.3 mmols ofepichlorohydrin. The selectivity was 67% based on the hydrogen peroxideand 85% on the allyl chloride.

What we claim is:

y 1. A catalyst system consisting essentially of a combination of (l) atleast one organic tin compound as a first component having at least onehydroxyl group or a coordination group capable of being converted to ahydroxyl group in the presence of water or hydrogen peroxide asrepresented by the formulas:

wherein each of R R R R R and R represents an alkyl group, aralkylgroup, phenyl group, phenoxy group, alkoxy group, hydrogen atom,carbonyl group, nitrile group, hydroxyl group, acyl group, halogengroup, or S-R wherein R represents an alkyl or phenyl group, and (2) asecond component selected from the group consisting of molybdenic acid,tungstic acid, selenic acid, boron tungstic acid, phosphorus molybdicacid, phosphorous tungstic acid, phosphorous vanadic acid, phosphorousselenic acid; and naphthenates, stearates, octoates, carbonyls,acetylacetonates, oxides, ammonium salts, phosphates, nitrates, sulfatesor carbonates of molybdenum, tungsten, vanadium or selenium; boric acid,boron trioxide, boronhydride, boron halides and boroxin substituted withalkoxy or al-kyl groups, the ratio of the second component to the firstcomponent being 1-0.001 to 1.

2. The catalyst system according to claim 1, wherein the ratio of tinatom of the first component to each of the elements of molybdenum,tungsten, vanadium, selenium or boron atom of the second component is10-100 to 1.

References Cited UNITED STATES PATENTS 2,833,788 5/ 1958 Skinner et al.260348.5 L 2,892,826 6/1959 Peters et al. 252-430 X 2,946,778 7/ 1960 Keet al. 252-430 X (Other references on following page) UNITED STATESPATENTS Steinmetz et a1. 252-431 R X Loeb 252-431 R X Jenkins 252-431 RX Wade 252-431 R X Allan 260-3485 L Larson 252-431 R X Larson 252-431 RX Kollar 252-430 X 14 FOREIGN PATENTS 788,951 1/ 1958 Great Britain252-431 R PATRICK P. GARVIN, Primary Examiner U.S. Cl. X.R.

252-428, 430, 431 R, 431 C, 431 N; 260-3485 L

